CN118223023A - Etching solution for copper thick film - Google Patents
Etching solution for copper thick film Download PDFInfo
- Publication number
- CN118223023A CN118223023A CN202410461294.1A CN202410461294A CN118223023A CN 118223023 A CN118223023 A CN 118223023A CN 202410461294 A CN202410461294 A CN 202410461294A CN 118223023 A CN118223023 A CN 118223023A
- Authority
- CN
- China
- Prior art keywords
- hydrogen peroxide
- etching
- etching solution
- copper
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000005530 etching Methods 0.000 title claims abstract description 221
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 239000010949 copper Substances 0.000 title claims abstract description 90
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 82
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 199
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000000126 substance Substances 0.000 claims abstract description 39
- 230000002378 acidificating effect Effects 0.000 claims abstract description 38
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 32
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 32
- -1 amine compound Chemical class 0.000 claims abstract description 31
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 21
- 239000003112 inhibitor Substances 0.000 claims abstract description 18
- 239000000243 solution Substances 0.000 claims description 134
- 239000012141 concentrate Substances 0.000 claims description 32
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 24
- 239000000758 substrate Substances 0.000 claims description 18
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 15
- 150000007524 organic acids Chemical class 0.000 claims description 15
- LUBJCRLGQSPQNN-UHFFFAOYSA-N 1-Phenylurea Chemical compound NC(=O)NC1=CC=CC=C1 LUBJCRLGQSPQNN-UHFFFAOYSA-N 0.000 claims description 13
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- XZGLNCKSNVGDNX-UHFFFAOYSA-N 5-methyl-2h-tetrazole Chemical compound CC=1N=NNN=1 XZGLNCKSNVGDNX-UHFFFAOYSA-N 0.000 claims description 10
- 239000012964 benzotriazole Substances 0.000 claims description 10
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 9
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 claims description 9
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 150000003851 azoles Chemical class 0.000 claims description 7
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 claims description 7
- 238000010790 dilution Methods 0.000 claims description 7
- 239000012895 dilution Substances 0.000 claims description 7
- LRUDIIUSNGCQKF-UHFFFAOYSA-N 5-methyl-1H-benzotriazole Chemical compound C1=C(C)C=CC2=NNN=C21 LRUDIIUSNGCQKF-UHFFFAOYSA-N 0.000 claims description 6
- 229940043276 diisopropanolamine Drugs 0.000 claims description 6
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000010408 film Substances 0.000 description 54
- 239000002994 raw material Substances 0.000 description 22
- 238000011156 evaluation Methods 0.000 description 15
- 239000003381 stabilizer Substances 0.000 description 14
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- 239000002253 acid Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- KJUGUADJHNHALS-UHFFFAOYSA-N 1H-tetrazole Substances C=1N=NNN=1 KJUGUADJHNHALS-UHFFFAOYSA-N 0.000 description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 5
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 5
- 229910052750 molybdenum Inorganic materials 0.000 description 5
- 239000011733 molybdenum Substances 0.000 description 5
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 4
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N 1H-imidazole Chemical compound C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 235000001014 amino acid Nutrition 0.000 description 3
- 229940024606 amino acid Drugs 0.000 description 3
- 150000001413 amino acids Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000010494 dissociation reaction Methods 0.000 description 3
- 230000005593 dissociations Effects 0.000 description 3
- 238000005401 electroluminescence Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000001630 malic acid Substances 0.000 description 3
- 235000011090 malic acid Nutrition 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 150000003536 tetrazoles Chemical class 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 150000003852 triazoles Chemical class 0.000 description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 2
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- LSBDFXRDZJMBSC-UHFFFAOYSA-N 2-phenylacetamide Chemical compound NC(=O)CC1=CC=CC=C1 LSBDFXRDZJMBSC-UHFFFAOYSA-N 0.000 description 2
- QMHIMXFNBOYPND-UHFFFAOYSA-N 4-methylthiazole Chemical compound CC1=CSC=N1 QMHIMXFNBOYPND-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 2
- 239000004471 Glycine Substances 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- BTCSSZJGUNDROE-UHFFFAOYSA-N gamma-aminobutyric acid Chemical compound NCCCC(O)=O BTCSSZJGUNDROE-UHFFFAOYSA-N 0.000 description 2
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- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
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- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 2
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- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 239000004474 valine Substances 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/10—Other heavy metals
- C23G1/103—Other heavy metals copper or alloys of copper
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
- H05K3/067—Etchants
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- ing And Chemical Polishing (AREA)
- Weting (AREA)
Abstract
Providing: the etching solution for copper thick film has a high etching rate and can be etched even at a high copper ion concentration to thicken the copper film thickness so that the conventional production rate can be maintained. The etching solution for copper thick films, which comprises hydrogen peroxide, a strongly acidic substance, an amine compound, a hydrogen peroxide decomposition inhibitor, an azole and water and has a pH of less than 2, can etch a copper film at an etching rate of 380 nm/min or more even at a high copper ion concentration of 20000ppm, and further can adjust the taper angle to 30 DEG to 80 deg.
Description
The application is a divisional application of application No. 201880002496.2, with application No. 2018, 3-23 and application name of etching liquid for copper thick film.
Technical Field
The present invention relates to an etching solution for a copper thick film used for etching copper used for wiring of a flat panel display such as a liquid crystal or an organic EL.
Background
A TFT (thin film transistor Thin Film Transistor) of a Flat Panel Display (FPD) such as a liquid crystal or an organic EL (Electro-Luminescence) device uses aluminum as a wiring material. In recent years, FPDs with a large screen and high definition have been widely used, and a wiring material used for the FPD is required to have a lower resistance than aluminum. Therefore, copper having a lower resistance than aluminum has been used as a wiring material in recent years.
The wiring of the FPD is formed by wet etching a copper film formed by a sputtering method. This is because the process can be shortened by forming a large area at one time. In this case, the following points are important in wet etching of the wiring.
(1) The processing precision is high and the same.
(2) The processed wiring section is in a regular cone shape with a prescribed angle.
(3) The etching rate is not changed by containing copper ions (bath life is long).
Patent document 1 discloses an etching solution satisfying such a requirement.
Disclosed herein is an etching solution for a multilayer film containing molybdenum and copper, which is characterized by comprising:
Hydrogen peroxide,
An acidic organic acid,
An amine compound,
A hydrogen peroxide decomposition inhibitor,
Azoles, and
An aluminum salt-containing precipitation inhibitor.
The etching solution has performance satisfying the level used in current production in evaluation of copper (Cu) and molybdenum (Mo) etching rate, taper angle of etched boundary region, side etching of molybdenum (Mo), residue of molybdenum (Mo), resistance to overetch, precipitate, hydrogen peroxide decomposition rate, and the like.
Further, for the same purpose, patent document 2 discloses an etching solution for a multilayer thin film including a copper layer and a molybdenum layer, which includes: (A) hydrogen peroxide; (B) a mineral acid containing no fluorine atom; (C) An organic acid selected from at least one of succinic acid, glycolic acid, lactic acid, malonic acid and malic acid; (D) An amine compound having 2 to 10 carbon atoms and having an amino group and a hydroxyl group such that the total number of groups is two or more; (E) 5-amino-1H-tetrazole; and (F) a hydrogen peroxide stabilizer, the pH being from 2.5 to 5.
Prior art literature
Patent literature
Patent document 1: japanese patent application laid-open No. 2015-209868
Patent document 2: japanese patent 5051323
Disclosure of Invention
Problems to be solved by the invention
High resolution standards such as 4K, 8K are currently advocated. These standards cannot exert their ability in small pictures. Accordingly, a display (large screen FPD) having a larger screen than the conventional one has been developed. In a large-screen FPD, the distance of the wiring for driving the pixels becomes long, and thus, a wiring having a lower resistance is required. In order to reduce the resistance in copper wiring, it is considered to increase the cross-sectional area of the wiring. However, if the width of the wiring is increased and the area of 1 pixel is increased, the requirement for high definition or the like cannot be satisfied.
On the other hand, in order to reduce the resistance of the wiring material, it is considered to use a material having a lower resistivity than copper, such as silver or gold, but the cost is excessively high, which is not preferable from the viewpoint of popularization. As a result, it is necessary to increase the sectional area or decrease the resistance value by increasing the thickness direction of the copper wiring.
In order to form a wiring having a thickened copper thickness, the following technical problems must be solved.
(1) In order to maintain the same manufacturing rate as before, the etching rate is increased.
(2) The amount of copper ions etched in the etching liquid increases, and therefore, etching can be performed even at a high copper ion concentration.
Solution for solving the problem
The present invention has been made in order to solve the above problems, and an object of the present invention is to provide an etchant for a copper thick film which has a high etching rate and does not require additional addition of an etchant for dilution at a copper ion concentration of 20000ppm or less.
More specifically, the etching solution for copper thick films of the present invention is characterized by comprising:
Hydrogen peroxide,
A strongly acidic substance,
An amine compound,
A hydrogen peroxide decomposition inhibitor,
Azoles, and
The water is used as the water source,
No additional etching solution for dilution was required until the copper ion concentration was 20000ppm,
And a pH below 2.
ADVANTAGEOUS EFFECTS OF INVENTION
The etching solution for copper thick films of the present invention has an etching rate of 380 nm/min or more as an etching rate. In addition, even if the copper ion concentration is 20000ppm, etching can be continued.
Therefore, the etching solution for copper thick films of the present invention has the following effects: when etching copper in a thick film state, the copper can be processed in a conventional process time without adding an etching solution for dilution until the copper ion concentration reaches 20000ppm, and etching can be continued even if copper ions remain in the etching solution at a high concentration.
Drawings
Fig. 1 is a conceptual diagram showing a cross section of an etched wiring.
Detailed Description
The etching liquid for copper thick film of the present invention will be described below. The following description shows an embodiment of the etching liquid of the present invention, and the following embodiments and examples may be modified within the scope of the present invention. In the following description, the terms "a to B" or "a to B" are used in the meaning of "a or more and B or less" when the numerical range is indicated. That is, it means a range including the value a and greater than the value a, and including the value B and less than the value B. In addition, "greater than a" means that no value a is contained and greater than a value a, and "lower than a" means that no value a is contained and less than a value a.
The etching solution for copper thick films of the present invention comprises: hydrogen peroxide, a strongly acidic substance, an amine compound, a hydrogen peroxide decomposition inhibitor, an azole and water, and an etching solution for dilution is not required to be added until the copper ion concentration is 20000ppm, and the pH is lower than 2. The components are described in detail below.
< Hydrogen peroxide >, a method for producing the same
For copper etching, copper is oxidized to form copper oxide (CuO), which is dissolved by an acid. That is, hydrogen peroxide is used as an oxidizing agent for oxidizing copper. Hydrogen peroxide (japanese: peracid water) is synonymous with hydrogen peroxide (japanese: water). The hydrogen peroxide is preferably 4.0 to 5.8 mass% of the total amount of the etching solution.
< Strongly acidic substance >)
The etching solution for copper thick film of the present invention has a pH of less than 2 in order to increase the etching rate. Therefore, a substance having strong acidity must be used. The strong acidic substance may be an inorganic strong acid or an organic strong acid. In addition, even if the etching solution is weakly acidic, the pH of the entire etching solution may be set to be lower than 2.
In general, the strength of an acid is represented by an acid dissociation constant Ka. The value of the negative logarithm of the acid dissociation constant Ka is referred to as pKa. The strongly acidic substance that can be used in the present invention may be a substance having a pKa of 3 or less, in addition to a substance called a strong acid having a pKa of zero or less. This is because the etching solution is mixed with a plurality of substances, but if the pKa is 3 or less, the pH of the entire etching solution can be adjusted to be lower than 2. Thus, in the present invention, a strongly acidic substance means a substance having a pKa of 3 or less.
Specifically, examples of the inorganic acid as a strongly acidic substance include hydrochloric acid, sulfuric acid, nitric acid, hydrobromic acid (aqueous solution of hydrogen bromide), hydroiodic acid (aqueous solution of hydrogen iodide), sulfamic acid, and the like.
In addition, as the organic acid of the strongly acidic substance, amino acids such as glycine, asparagine, aspartic acid, alanine, glutamic acid, valine, glutamine, glutamic acid, leucine, arginine, isoleucine, lysine, serine, histidine, threonine, phenylalanine, cysteine, tyrosine, methionine, tryptophan, and proline; malonic acid, pyruvic acid, oxalic acid, tartaric acid, trans-aconitic acid, p-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, vinylsulfonic acid, picric acid, trichloroacetic acid, acetamide, salicylic acid, 4-nitroaniline and the like.
Among the organic acids, those exhibiting strong acidity include those having halogen in the skeleton. In particular, there are strongly acidic substances such as trifluoroacetic acid. However, fluorine contained in the skeleton may be changed to hydrofluoric acid, and there is a concern that the substrate may be damaged, and therefore, it is desirable to exclude fluorine from the strongly acidic substance of the present invention.
The strongly acidic substance may be contained in an amount of 5 to 15 mass% based on the total amount of the etching solution. In order to adjust the etching target portion and the taper angle after etching, a chemical to be described later may be prepared so that the pH of the whole becomes lower than 2.
< Organic acid >
The etching solution for copper thick films of the present invention may contain a weakly acidic organic acid in addition to the strongly acidic substance, from the viewpoint of the effects such as adjusting the taper angle and suppressing the decomposition of hydrogen peroxide. Here, the weak acidity means a substance having an acid dissociation constant pKa of more than 3.
Specifically, the organic acid is preferably an amino acid having 1 to 10 carbon atoms, in addition to an aliphatic carboxylic acid having 1 to 18 carbon atoms and an aromatic carboxylic acid having 6 to 10 carbon atoms.
Preferred examples of the aliphatic carboxylic acid having 1 to 18 carbon atoms include formic acid, acetic acid, propionic acid, lactic acid, glycolic acid, diglycolic acid, butyric acid, hydroxybutyric acid, succinic acid, malic acid, maleic acid, fumaric acid, valeric acid, glutaric acid, itaconic acid, adipic acid, caproic acid, citric acid, propane tricarboxylic acid, heptanoic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, and linolenic acid.
Preferred examples of the aromatic carboxylic acid having 6 to 10 carbon atoms include benzoic acid, mandelic acid, phthalic acid, isophthalic acid, terephthalic acid and the like.
Further, preferred examples of the amino acid having 1 to 10 carbon atoms include carbamic acid, sarcosine, 4-aminobutyric acid, iminodibutyric acid, nitrilotriacetic acid, and the like. The weakly acidic organic acid may be contained in an amount of 1 to 20 mass% based on the total amount of the etching solution.
< Amine Compound >)
The amine compound plays a role in adjusting the taper angle of the copper film and adjusting the pH of the etching solution. As the amine compound, an amine compound having 2 to 10 carbon atoms can be suitably used. More specifically, preferred examples thereof include polyamines such as ethylenediamine, trimethylene diamine, tetramethylenediamine, 1, 2-propane diamine, 1, 3-propane diamine, N-dimethyl-1, 3-propane diamine, N-diethyl-1, 3-propane diamine, 1, 3-diaminobutane, 2, 3-diaminobutane, pentamethylene diamine, 2, 4-diaminopentane, hexamethylenediamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, N-methylethylenediamine, N-dimethylethylenediamine, trimethylethylenediamine, N-ethylethylenediamine, N-diethyl ethylenediamine, triethylethylenediamine, 1,2, 3-triaminopropane, hydrazine, tris (2-aminoethyl) amine, tetrakis (aminomethyl) methane, diethylenetriamine, triethylenetetramine, tetraethylpentamine, heptaethyleneoctamine, nonaethylenedecamine, diazabicycloundecene and the like; ethanolamine, N-methylethanolamine, N-methyldiethanolamine, N-ethylethanolamine, N-aminoethylethanolamine, N-propylethanolamine, N-butylethanolamine, diethanolamine, triethanolamine, 1-amino-2-propanol, N-methylisopropanolamine, N-ethylisopropanolamine, triisopropanolamine, diisopropanolamine, N-propylisopropanolamine, 2-aminopropane-1-ol, N-methyl-2-amino-propane-1-ol, N-ethyl-2-amino-propane-1-ol, 1-aminopropane-3-ol, N-methyl-1-aminopropane-3-ol, N-ethyl-1-aminopropane-3-ol, 1-aminobutan-2-ol, N-methyl-1-aminobutan-2-ol, N-ethyl-1-aminobutan-2-ol, 2-aminobutan-1-ol, N-methyl-2-aminobutan-1-ol, N-ethyl-2-aminobutan-1-ol, 3-aminobutan-1-ol, N-methyl-3-amino-1-aminobutan-3-ol, N-ethyl-1-aminobutan-4-amino-1-ethyl-2-ol, N-methyl-1-aminobutan-4-ol, N-ethyl-1-aminobutan-4-ol, 1-amino-2-methylpropan-2-ol, 2-amino-2-methylpropan-1-ol, 1-aminopentane-4-ol, 2-amino-4-methylpentane-1-ol, 2-aminohexane-1-ol, 3-aminoheptane-4-ol, 1-aminooctane-2-ol, 5-aminooctane-4-ol, 1-aminopropane-2, 3-diol, 2-aminopropane-1, 3-diol, tris (oxymethyl) aminomethane, 1, 2-diaminopropane-3-ol, 1, 3-diaminopropane-2-ol, 2- (2-aminoethoxy) ethanol, 2- (2-aminoethylamino) ethanol, diglycolamine and the like, which may be used singly or in combination of plural kinds.
Among them, 1-amino-2-propanol (CAS No. 78-96-6: hereinafter also referred to as "1A 2P"), N-diethyl-1, 3-propanediamine (CAS No. 104-78-9: hereinafter also referred to as "NNDPA"), triisopropanolamine (CAS No. 122-20-3: hereinafter also referred to as "TIPA"), and diisopropanolamine (CAS No. 110-97-4: hereinafter also referred to as "DIPA") are particularly preferable. The amine compound is preferably contained in an amount of 0.05 to 5.5% by mass based on the total amount of the etching solution.
< Hydrogen peroxide decomposition inhibitor >)
In the etching solution for copper thick films of the present invention, hydrogen peroxide is used as the oxidizing agent. Hydrogen peroxide itself is decomposed, and therefore a decomposition inhibitor for inhibiting the decomposition thereof is added. The hydrogen peroxide decomposition inhibitor is also called a hydrogen peroxide (Japanese: peracid water) stabilizer (or "hydrogen peroxide (Japanese: water-passing) stabilizer").
As the hydrogen peroxide decomposition inhibitor, in addition to urea-based hydrogen peroxide decomposition inhibitors such as urea, phenylurea, allylurea, 1, 3-dimethylurea, thiourea, etc., lower alcohols such as phenylacetamide, phenylglycol, 1-propanol, 2-propanol, etc., ethylene glycol monobutyl ether, etc., can be used. Among them, urea (CAS No. 57-13-6), phenylurea (CAS No. 64-10-8: hereinafter also referred to as "FN"), 1-propanol (CAS No. 71-23-8: hereinafter also referred to as "1P"), and ethylene glycol monobutyl ether (CAS No. 111-76-2: hereinafter also referred to as "BG") are particularly preferable. The hydrogen peroxide decomposition inhibitor is preferably contained in an amount of 0.1 to 2.0 mass% relative to the total amount of the etching solution.
< Azoles >)
The etching solution for copper thick films of the present invention contains an azole in order to suppress the etching rate of Cu. In the etching solution for copper thick films of the present invention, the pH is set to be less than 2 in order to increase the etching rate. In this region of pH, the etching rate changes sharply according to a slight difference in pH. In this way, the etching rate cannot be adjusted only by the composition ratio of the strongly acidic substance. Thus, inhibitors of etch rate are utilized.
As the azole, triazoles, tetrazoles, imidazoles, thiazoles, and the like can be suitably used. More specifically, the following examples are given. As the triazole, 1H-benzotriazole, 5-methyl-1H-benzotriazole, 3-amino-1H-triazole and the like can be suitably used.
As tetrazoles, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, and the like can be suitably used. As the imidazoles, 1H-imidazole, 1H-benzimidazole, and the like can be suitably used. As the thiazole, 1, 3-thiazole, 4-methylthiazole and the like can be suitably used.
Among them, tetrazoles have a high effect of suppressing the etching rate, particularly preferably 5-amino-1H-tetrazole (CAS No. 4418-61-5: hereinafter also referred to as "5A1 HT"), 5-methyl-1H-tetrazole (CAS No. 4076-36-2: hereinafter also referred to as "5M1 HT"), 5-phenyl-1H-tetrazole (CAS No. 18039-42-4: hereinafter also referred to as "5 phenyl 1 HT"), and triazoles, particularly preferably 5-methyl-1H-benzotriazole (CAS No. 136-85-6: hereinafter also referred to as "5M1 HBTA"), 1H-benzotriazole (CAS No. 95-14-7: hereinafter also referred to as "BTA").
These azoles are preferably contained in an amount of 0.01 to 0.10 mass% based on the total amount of the etching solution.
< Copper ion >
The copper etching solution is added with a diluting etching solution so that the concentration of Cu ions is usually about 2000ppm to 4000 ppm. This is because, when the copper ion concentration increases, the decomposition rate of hydrogen peroxide increases, and thus the hydrogen peroxide concentration in the etching solution decreases. However, since the etching solution of the present invention uses the hydrogen peroxide decomposition inhibitor in an acidic environment, the decomposition rate of hydrogen peroxide is suppressed. Therefore, even if a higher Cu ion concentration is formed, the addition of an etching solution for diluting Cu ions is not required. More specifically, the addition of the diluted etching solution is not required until the Cu concentration of the etching solution is 20000 ppm.
< Others >
In addition to these components, water and various additives that are generally used in a range that does not inhibit etching performance may be added to the etching solution for copper thick films of the present invention. For precision machining purposes, it is preferable that no foreign matter is present in the water. Preferably pure water or ultrapure water. Water may be determined as a residual component relative to the above components.
It is needless to say that the content ratio of each component described above is appropriately adjusted so as to be 100 mass% based on the total amount of the etching solution. Further, copper ions may be contained from the beginning but in a smaller amount relative to other compositions, and therefore the composition ratio based on the total amount of the etching liquid is disregarded.
< PH, temperature >
The etching solution for copper thick film of the present invention is adjusted to a pH of less than 2. The etching solution may be used at 20 to 40 ℃. More preferably from 25℃to 35℃and most preferably from 30℃to 35 ℃.
< Save >)
The etching liquid for copper thick film of the present invention uses hydrogen peroxide. The hydrogen peroxide itself decomposes. Therefore, the etching solution contains a hydrogen peroxide decomposition inhibitor. But at the time of preservation, hydrogen peroxide (or hydrogen peroxide solution) and other liquids may be preserved separately. The hydrogen peroxide solution is an aqueous hydrogen peroxide solution. In addition, only hydrogen peroxide (or hydrogen peroxide solution), water, and a raw material other than copper ions (referred to as "etching solution raw material") may be collectively stored. The etching liquid material may be a liquid material or a powder material. That is, the etching solution for copper thick films of the present invention can be completed by combining an etching solution raw material, water, and hydrogen peroxide (or hydrogen peroxide solution).
Alternatively, the etching solution raw material and water may be mixed to prepare a solution of the etching solution raw material. The solution of the etching solution raw material prepared by using the etching solution raw material and water is referred to as "etching concentrate". The etching concentrated solution is free of hydrogen peroxide and has a smaller volume than the etching solution, and therefore is convenient to store and transfer. Thus, the etching solution for copper thick films of the present invention can be completed by combining an etching concentrate, water and hydrogen peroxide.
Here, the water in the etching concentrate may be present in an amount to dissolve only the etching liquid raw material. In other words, the water in the etching concentrate may be less than the water in the etching solution. Therefore, considering that hydrogen peroxide is supplied as a hydrogen peroxide solution as an aqueous solution, the etching solution for copper thick films of the present invention can be completed by combining three of an etching concentrate, water and a hydrogen peroxide solution.
If water is contained in the etching concentrate or the hydrogen peroxide solution, the etching concentrate and the hydrogen peroxide solution may be combined. In the present specification, the ratio of each component of the etching concentrate is expressed as a ratio relative to the total amount of the etching concentrate at the time of completion. Therefore, the total of the components of the etching concentrate is not 100 mass%.
Etching method
The etching solution for copper thick film of the present invention is used for forming a copper film having a thickness of 600nm or more on a substrate. An isolation layer formed of other elements may be formed between the substrate and the copper film. The etching method of the present invention is performed by bringing a substrate having a copper film formed at a thickness of 600nm or more into contact with an etching liquid for a copper thick film.
The etching solution for copper thick films of the present invention can be stored for a long period of time by separating hydrogen peroxide, etching solution raw materials (or etching concentrate) and water at the time of storage. Therefore, in actual use, the etching solution is prepared. The method of preparing the hydrogen peroxide is not limited as long as the final hydrogen peroxide concentration is a predetermined concentration.
An example of the method is described below, in which an etching concentrate is produced by mixing an etching solution raw material with a predetermined amount of water. The hydrogen peroxide is generally supplied in the form of a hydrogen peroxide solution having a concentration higher than that of the etching solution for copper thick films of the present invention. Thus, a hydrogen peroxide solution and an etching concentrate were prepared in predetermined amounts. This step may be referred to as a step of preparing an etching solution for a copper thick film. The prepared etching solution for copper thick film was prepared so that the pH was lower than 2 by adjusting the respective components to a predetermined ratio.
In the etching, as described above, the etching solution is used under the conditions that the pH is lower than 2 and the temperature is 20 to 40 ℃. Therefore, the etched object is also preferably heated to the temperature by the waste heat. The method for bringing the substrate into contact with the etching solution is not particularly limited. The etching liquid may be dispersed from above on the substrate to be processed as in the shower, or the substrate to be processed may be immersed in a bath of the etching liquid. This step may be referred to as a step of bringing the etching liquid for copper thick film into contact with the substrate to be processed.
The substrate to be processed is a substrate in which at least a copper film is formed on a base material such as glass, and a resist pattern for patterning is formed on the copper film.
Examples
Description of various evaluation methods
The etching solution for copper thick films of the present invention was evaluated in terms of copper etching rate (nm/min), taper angle (°) of the cross section of the etched wiring, and shape after etching.
The etching rate was measured as follows. First, a copper film was formed at a thickness of 600nm by sputtering on a silicon wafer having a thermal oxide film of 100nm formed thereon. The copper film is brought into contact with an etching solution at 30 ℃ (35 ℃ in some cases according to the comparative example) for 20 seconds to 60 seconds.
The resistance values of the films before and after etching were measured using a constant current application type 4-terminal 4-probe resistivity meter (Mitsubishi CHEMICAL ANALYTECH co., ltd.: MCP-T610). The film thickness change and the etching rate were calculated from the change in the resistance value.
If the etching rate of copper is 380 nm/min or more, it is determined as a circle (good) as described above. In addition, the fork was judged to be out of the predetermined range (X).
It should be noted that "circle" refers to a standard range, success or pass, and "cross" refers to a standard range, failure or fail. The same applies to the following evaluation.
The cone angle was measured as follows. First, a thick copper film was formed on a glass substrate by sputtering to a thickness of 600nm as a copper film, and a thick copper film sample was produced. A resist layer patterned in a wiring shape was formed on the copper film as a base material for taper angle evaluation. That is, the substrate includes a substrate, a copper film, and a patterned resist layer on the copper film. The substrate is immersed in an etching solution for a suitable etching (Just etching) time period, and is etched. After washing and drying the etched sample, the wiring portion was cut off, and the cut surface was observed.
The observation of the cut surface was performed under the conditions of acceleration voltage of 1kV and 30000 to 50000 times by using SEM (Hitachi-Tex.: SU8020 type). In the SEM observation, the shape of the etched portion was also observed. The appropriate etching is a time from the start of etching until the film transmits light. The time at which the film transmitted light was visually confirmed.
A schematic diagram of the cut surface shape is shown in fig. 1. As shown in fig. 1, an angle 3 formed by the substrate 1 and the etched inclined surface 5 is set to be a taper angle (°). If the taper angle 3 is 30 ° to 80 °, it is determined as a circle (∈circle). If the angle is out of the range, it is determined as fork (X). In fig. 1, a Cu layer is denoted by a reference numeral 2, and a resist layer is denoted by a reference numeral 4.
Example 1
8.33% By mass of nitric acid as a strongly acidic substance is contained
NNDPA.24% by mass of (N, N-diethyl-1, 3-propanediamine) as an amine compound
FN (phenylurea) as hydrogen peroxide stabilizer 0.12 mass%
5M1HT (5-methyl-1H-tetrazole) 0.01 mass% as azole
The etching solution raw material was prepared with water 72.41 mass%, and an etching concentrate was prepared. The ratio of each component in the etching concentrated solution is expressed as a ratio relative to the total amount of the etching solution when the etching solution is mixed with a hydrogen peroxide solution described later. The same applies to the following examples and comparative examples.
13.89 Mass% of the 35% hydrogen peroxide solution (4.86 mass% hydrogen peroxide and 9.03 mass% water based on the total amount of the etching solution) was mixed with the etching concentrate to prepare an etching solution having a hydrogen peroxide concentration of 4.86 mass%. The total amount of water was 81.44% by mass. Further, copper powder was added to adjust the copper ion concentration to 20000ppm. In addition, the use is carried out at a liquid temperature of 35 ℃. Table 1 shows the concentrations of the components and the results of the evaluation items in the entire etching solution.
Example 2
Comprises 9.88 mass% of malonic acid as a strongly acidic substance,
1.35% By mass of 1A2P (1-amino-2-propanol) as an amine compound,
0.68% By mass of 1P (1-propanol) as a stabilizer for hydrogen peroxide,
5A1HT (5-amino-1H-tetrazole) 0.05 mass% as azole
An etching concentrate was prepared by mixing 75.70 mass% of water with the etching solution raw material.
The 35% hydrogen peroxide solution (12.34% by weight of hydrogen peroxide, 4.32% by weight of hydrogen peroxide, and 8.02% by weight of water based on the total amount of the etching solution) was mixed with the etching concentrate to prepare an etching solution having a hydrogen peroxide concentration of 4.32% by weight. The total amount of water was 83.72% by mass. Further, copper powder was added to adjust the copper ion concentration to 20000ppm. In addition, the use is carried out at a liquid temperature of 35 ℃. Table 1 shows the concentrations of the components and the results of the evaluation items in the entire etching solution.
Example 3
Will contain 6.93 mass% sulfuric acid as a strongly acidic substance
Glycine 1.84 mass%
TIPA (triisopropanolamine) as amine Compound 2.49% by mass
Urea 0.64 mass% as hydrogen peroxide stabilizer
5M1HBTA (5-methyl-1H-benzotriazole) as azole 0.03% by mass
73.36 Mass% of water, to prepare an etching concentrate.
The 35% hydrogen peroxide solution (14.71% by weight, 5.15% by weight of hydrogen peroxide and 9.56% by weight of water based on the total amount of the etching solution) was mixed with the etching concentrate to prepare an etching solution having a hydrogen peroxide concentration of 5.15% by weight. The total amount of water was 82.92% by mass. Further, copper powder was added to adjust the copper ion concentration to 20000ppm. In addition, the use is carried out at a liquid temperature of 35 ℃. Table 1 shows the concentrations of the components and the results of the evaluation items in the entire etching solution.
Example 4
7.20 Mass% of malonic acid as a strongly acidic substance,
Glutaric acid as organic acid 6.77% by mass
DIPA (diisopropanolamine) as amine Compound 0.06% by mass
0.96 Mass% of BG (ethylene glycol monobutyl ether) as a hydrogen peroxide stabilizer,
5 Phenyl 1HT (5-phenyl-1H-tetrazole) 0.03 mass% as azole
The etching solution raw material of (2) was prepared by mixing with water 70.32% by mass.
The 35% hydrogen peroxide solution (14.66% by weight, 5.13% by weight of hydrogen peroxide and 9.53% by weight of water based on the total amount of the etching solution) was mixed with the etching concentrate to prepare an etching solution having a hydrogen peroxide concentration of 5.13% by weight. The total amount of water was 79.85 mass%. Further, copper powder was added to adjust the copper ion concentration to 20000ppm. In addition, the use is carried out at a liquid temperature of 35 ℃. Table 1 shows the concentrations of the components and the results of the evaluation items in the entire etching solution.
Example 5
7.04% By mass of ethanesulfonic acid as a strongly acidic substance
Malic acid as organic acid 4.4% by mass
TIPA (triisopropanolamine) as amine Compound 1.04% by mass
0.85 Mass% of BG (ethylene glycol monobutyl ether) as a hydrogen peroxide stabilizer,
BTA (benzotriazole) as azole 0.02% by mass
The etching solution raw material of (2) was prepared by mixing 71.56 mass% of water with the etching solution raw material of (2) to prepare an etching concentrate.
The 35% hydrogen peroxide solution (15.09% by weight, 5.28% by weight of hydrogen peroxide and 9.81% by weight of water based on the total amount of the etching solution) was mixed with the etching concentrate to prepare an etching solution having a hydrogen peroxide concentration of 5.28% by weight. The total amount of water was 81.37% by mass. Further, copper powder was added to adjust the copper ion concentration to 20000ppm. In addition, the use is carried out at a liquid temperature of 35 ℃. Table 1 shows the concentrations of the components and the results of the evaluation items in the entire etching solution.
Example 6
7.04% By mass of ethanesulfonic acid as a strongly acidic substance
TIPA (triisopropanolamine) as amine Compound 1.04% by mass
0.85 Mass% of BG (ethylene glycol monobutyl ether) as a hydrogen peroxide stabilizer,
BTA (benzotriazole) as azole 0.02% by mass
The etching solution raw material of (2) was prepared by mixing with water 75.96% by mass.
The 35% hydrogen peroxide solution (15.09% by weight, 5.28% by weight of hydrogen peroxide and 9.81% by weight of water based on the total amount of the etching solution) was mixed with the etching concentrate to prepare an etching solution having a hydrogen peroxide concentration of 5.28% by weight. The total amount of water was 85.77% by mass. Further, copper powder was added to adjust the copper ion concentration to 20000ppm. In addition, the use is carried out at a liquid temperature of 35 ℃. Table 1 shows the concentrations of the components and the results of the evaluation items in the entire etching solution.
Comparative example 1
10.00 Mass% of nitric acid as a strongly acidic substance is contained
NNDPA (N, N-diethyl-1, 3-propanediamine) as amine compound 12.50% by mass
FN (phenylurea) as hydrogen peroxide stabilizer 0.10 mass%
5M1HT (5-methyl-1H-tetrazole) 0.10 mass% as azole
The etching solution raw material of (2) was prepared by mixing with water 65.87% by mass.
An etching solution having a hydrogen peroxide concentration of 4.00 mass% was prepared by mixing 11.43 mass% of a 35% hydrogen peroxide solution (4.00 mass% hydrogen peroxide and 7.43 mass% water) with the etching concentrate. The total amount of water was 73.30% by mass. Further, the addition of copper powder was intended to dissolve the copper ion concentration to 20000ppm, but not completely dissolved. In addition, the use is carried out at a liquid temperature of 35 ℃. Table 2 shows the concentrations of the components and the results of the evaluation items in the entire etching solution.
Comparative example 2
Will contain 6.00 mass% of ethanesulfonic acid as a strongly acidic substance
9.70% By mass of TIPA (triisopropanolamine) as an amine compound
BG (ethylene glycol monobutyl ether) as hydrogen peroxide stabilizer 0.70 mass%
BTA (benzotriazole) as azole 0.02% by mass
The etching solution raw material of (2) was prepared by mixing with water 68.49% by mass.
The 35% hydrogen peroxide solution (15.09% by weight, 5.28% by weight of hydrogen peroxide and 9.81% by weight of water based on the total amount of the etching solution) was mixed with the etching concentrate to prepare an etching solution having a hydrogen peroxide concentration of 5.28% by weight. The total amount of water was 78.30 mass%. Further, the addition of copper powder was intended to dissolve the copper ion concentration to 20000ppm, but not completely dissolved. In addition, the use is carried out at a liquid temperature of 35 ℃. Table 2 shows the concentrations of the components and the results of the evaluation items in the entire etching solution.
Comparative example 3
15.80 Mass% of malonic acid as a strongly acidic substance is contained
8.40% By mass of 1A2P (1-amino-2-propanol) as an amine compound
1P (1-propanol) as Hydrogen peroxide stabilizer 0.60% by mass
5A1HT (5-amino-1H-tetrazole) 0.05 mass% as azole
The etching solution raw material of (2) was prepared by mixing with water 62.86% by mass.
The 35% hydrogen peroxide solution (12.29% by weight of hydrogen peroxide, 4.30% by weight of hydrogen peroxide, and 7.99% by weight of water based on the total amount of the etching solution) was mixed with the etching concentrate to prepare an etching solution having a hydrogen peroxide concentration of 4.30% by weight. The total amount of water was 70.85% by mass. Further, copper powder was added so that the copper ion concentration was 1000ppm. In addition, the use is carried out at a liquid temperature of 35 ℃. Table 2 shows the concentrations of the components and the results of the evaluation items in the entire etching solution.
Comparative example 4
6.90 Mass% of nitric acid as a strongly acidic substance is contained
NNDPA (N, N-diethyl-1, 3-propanediamine) as amine compound 8.34% by mass
FN (phenylurea) as hydrogen peroxide stabilizer 0.10 mass%
5M1HT (5-methyl-1H-tetrazole) 0.10 mass% as azole
The etching solution raw material of (2) was prepared by mixing 71.99 mass% of water with the etching solution raw material of (3) to prepare an etching concentrate.
The 35% hydrogen peroxide solution (12.57% by weight of hydrogen peroxide, 4.40% by weight of hydrogen peroxide, and 8.17% by weight of water based on the total amount of the etching solution) was mixed with the etching concentrate to prepare an etching solution having a hydrogen peroxide concentration of 4.40% by weight. The total amount of water was 80.16 mass%. Further, the addition of copper powder was intended to dissolve the copper ion concentration to 1000ppm, but not completely. In addition, the use is carried out at a liquid temperature of 35 ℃. Table 2 shows the concentrations of the components and the results of the evaluation items in the entire etching solution.
Comparative example 5
Will contain 6.00 mass% of ethanesulfonic acid as a strongly acidic substance
TIPA (triisopropanolamine) as an amine compound 5.96% by mass
BG (ethylene glycol monobutyl ether) as hydrogen peroxide stabilizer 0.82 mass%
BTA (benzotriazole) as azole 0.04% by mass
The etching solution raw material of (2) was prepared by mixing with water 72.09% by mass.
The 35% hydrogen peroxide solution (15.09% by weight, 5.28% by weight of hydrogen peroxide and 9.81% by weight of water based on the total amount of the etching solution) was mixed with the etching concentrate to prepare an etching solution having a hydrogen peroxide concentration of 5.28% by weight. The total amount of water was 81.90 mass%. Further, the addition of copper powder was intended to dissolve the copper ion concentration to 1000ppm, but not completely. In addition, the use is carried out at a liquid temperature of 35 ℃. Table 2 shows the concentrations of the components and the results of the evaluation items in the entire etching solution.
TABLE 1
TABLE 2
Referring to table 1, when an inorganic acid or an organic acid is used, the pH of the entire etching solution may be adjusted to be lower than 2 as long as the etching solution is a strongly acidic substance. The etching solution for a copper thick film thus produced can achieve an etching rate of 380 nm/min or more in a copper ion environment of 20000 ppm. In addition, the cone angle can be adjusted to 30-80 degrees. In addition, the shape is not particularly problematic.
On the other hand, refer to table 2. The materials used were the same as those in the examples shown in Table 1, but if the pH of the entire etching solution was not set to be lower than 2, the ion concentration would not be as high as 20000 ppm. Copper ions cannot be dissolved, and thus etching cannot be performed.
In the case where the strongly acidic substance is constituted only by an organic acid, the amine compound is preferably 0.05 mass% or more and less than 2.0 mass% (see examples 2, 4, 5, and 6). This is considered to be because the strongly acidic substance of the organic acid has a pKa higher than that of the inorganic acid, and therefore, if the amine compound is excessively added, the pH of the entire etching solution cannot be made lower than 2.
As described above, the etching solution for copper thick film of the present invention can realize a high etching rate even at a high copper ion concentration, and can etch thick film copper on a large-area substrate at a processing speed of a practical mass production machine.
Industrial applicability
The etching solution of the present invention can be suitably used for etching a copper film having a thickness of 600nm or more.
Description of the reference numerals
1. Substrate board
2 Cu layers
3. Taper angle
4. Resist layer
5. Inclined surface
Claims (8)
1. An etching solution for copper thick films, comprising:
Hydrogen peroxide,
A strongly acidic substance,
An amine compound,
A hydrogen peroxide decomposition inhibitor,
Azoles, and
The water is used as the water source,
No additional etching solution for dilution was required until the copper ion concentration was 20000ppm,
And a pH below 2.
2. The etching solution for a copper thick film according to claim 1, further comprising a weakly acidic organic acid.
3. The etching solution for copper thick films according to claim 1 or 2, wherein the azole is 1 or more selected from the group consisting of 5-amino-1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-methyl-1H-benzotriazole and benzotriazole.
4. The etching solution for a copper thick film according to any one of claims 1 to 3, wherein the amine compound is 1 or more selected from the group consisting of 1-amino-2-propanol, N-diethyl-1, 3-propanediamine, triisopropanolamine and diisopropanolamine.
5. The etching solution for a copper thick film according to any one of claims 1 to 4, wherein the hydrogen peroxide decomposition inhibitor is 1 or more selected from urea, phenylurea, 1-propanol, ethylene glycol monobutyl ether.
6. An etching concentrate for copper thick films comprising:
a strongly acidic substance,
An amine compound,
A hydrogen peroxide decomposition inhibitor,
Azoles, and
Water, and does not contain hydrogen peroxide,
No additional etching solution for dilution was required until the copper ion concentration was 20000ppm,
Adding hydrogen peroxide to form 4.0-5.8 wt%,
Whereby the pH becomes lower than 2.
7. The etching concentrate for a copper thick film according to claim 6, further comprising a weakly acidic organic acid.
8. An etching method for a copper thick film, comprising the steps of:
A step of adding hydrogen peroxide to the etching concentrate for copper thick film to form 4.0 to 5.8 mass% of the whole, thereby preparing the etching solution for copper thick film,
The etching concentrated solution for copper thick films comprises:
a strongly acidic substance,
An amine compound,
A hydrogen peroxide decomposition inhibitor,
Azoles, and
The water is used as the water source,
Adding hydrogen peroxide to form 4.0-5.8 wt%,
Thus, the etching solution for dilution was not required to be added until the copper ion concentration was 20000ppm, and the pH was lower than 2; and, a step of, in the first embodiment,
And a step of bringing a substrate having a copper film formed at a thickness of 600nm or more into contact with the etching liquid for a copper thick film.
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| PCT/JP2018/011695 WO2019180915A1 (en) | 2018-03-23 | 2018-03-23 | Etching liquid for thick copper film |
| CN201880002496.2A CN109415818A (en) | 2018-03-23 | 2018-03-23 | Copper thick film etching solution |
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| CN110904456B (en) * | 2019-12-28 | 2022-01-14 | 上海天承化学有限公司 | Copper etching solution and preparation method and application thereof |
| CN111647889A (en) * | 2020-05-27 | 2020-09-11 | 湖北兴福电子材料有限公司 | Copper etching solution with stable etching rate |
| JP2021195572A (en) * | 2020-06-09 | 2021-12-27 | メック株式会社 | Etching agent and etching method |
| CN112981405B (en) * | 2021-02-23 | 2022-11-15 | 江苏艾森半导体材料股份有限公司 | Titanium-tungsten etching solution and preparation method and application thereof |
| CN113215579B (en) * | 2021-03-11 | 2024-01-16 | 中国科学院近代物理研究所 | Surface treatment method for radio frequency four-stage field acceleration cavity |
| CN113079628A (en) * | 2021-03-30 | 2021-07-06 | 东莞市科佳电路有限公司 | Processing method of resistance copper foil material for mobile phone vibration motor PCB |
| CN113445052A (en) * | 2021-07-28 | 2021-09-28 | 南通群安电子材料有限公司 | Differential etching solution suitable for MSAP (multiple-site-sensitive protection) process |
| CN114016031B (en) * | 2021-10-22 | 2024-05-17 | 深圳市松柏实业发展有限公司 | Quick etching liquid and preparation method thereof |
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| CN115287657A (en) * | 2022-07-09 | 2022-11-04 | 南通群安电子材料有限公司 | Etching liquid medicine for cleaning copper teeth |
| WO2024038697A1 (en) * | 2022-08-19 | 2024-02-22 | 株式会社Adeka | Composition, etching method, and laminate manufacturing method |
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